JPH0610755B2 - Silver halide photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention a. INDUSTRIAL APPLICABILITY In the present invention, at least one of blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers is composed of a plurality of layers having different sensitivities, and the plurality of layers are viewed from the support side. The present invention relates to a photographic light-sensitive material comprising a low-sensitivity layer and a high-sensitivity layer which are sequentially arranged, and at least one silver halide emulsion layer having different color sensitivities is disposed between these layers.

B. 2. Description of the Related Art In recent years, the demand for silver halide emulsions for photography has become more and more stringent, and higher levels of photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density and sufficiently wide exposure range have been achieved. There is a demand.

In response to these requirements, a silver iodobromide emulsion containing 0 to 10 mol% of iodine is well known as a high-sensitivity emulsion. The conventional methods for preparing these emulsions are pH conditions such as ammonia method, neutral method and acidic method, and p
As a method of controlling the Ag condition and a mixing method, a single jet method, a double jet method and the like are known.

On the basis of these known techniques, technical means have been delicately studied and put to practical use for the purpose of achieving higher sensitivity, improvement of graininess, high sharpness and low fog. In the silver iodobromide emulsion targeted by the present invention,
Emulsions in which not only the crystal habit and the grain size distribution but also the concentration distribution of iodine in individual silver halide grains are controlled have been studied.

The most legitimate way to achieve photographic performance such as high sensitivity, excellent graininess, high sharpness, and low fog density as described above is to improve the quantum efficiency of silver halide. For this purpose, knowledge of solid state physics, etc. is being actively incorporated. A study in which the quantum efficiency is theoretically calculated and the effect of particle size distribution is considered is described in, for example, the 1980 Tokyo Symposium's proceedings "Interactions Between Lights and Materials", page 91. Has been done. According to this study
It is predicted that narrowing the grain size distribution and making a monodisperse emulsion is effective in improving quantum efficiency.
In addition, in order to achieve the sensitization of the silver halide emulsion, in a process called chemical sensitization which will be described in detail later, in order to efficiently achieve high sensitivity while maintaining low fog, monodispersion The reasoning that emulsions would be advantageous would also be reasonable.

To industrially produce a monodisperse emulsion, JP-A-54-4852 is used.
As described in Japanese Patent Laid-Open No. 1-44, it is necessary to control the theoretically determined supply rate of silver ions and halogen ions to the reaction system and sufficient stirring conditions under strict control of pAg and pH. To be done. The silver halide emulsion produced under these conditions has a cubic, octahedral or tetradecahedral shape, that is, it has (100) and (111) faces in various proportions. It consists of so-called normal crystal grains.
It is known that such normal crystal grains can increase the sensitivity.

On the other hand, conventionally, a silver iodobromide emulsion composed of polydispersed twin grains has been known as a silver halide emulsion suitable for a high speed photographic film.

Further, JP-A-58-113927 and others disclose silver iodobromide emulsions containing tabular twinned grains.

On the other hand, it is disclosed in Japanese Patent Laid-Open No. 53-22408 that the development activity is enhanced and the sensitivity is enhanced by a laminated type silver halide grain in which a plurality of outer shells (shells) are applied to the outside of the inner core. Kokoku 43-13162, J. Photo.Sci., 24 , 198 (1
976) etc.

Further, a silver halide grain having a coating layer provided by halogen substitution as the outermost layer of the silver halide grain is described in West German Patent 29
32650, JP-A-51-2417, JP-A-51-17436,
Although described in JP-A No. 52-11927, these silver halide grains may increase the fixing speed,
On the contrary, it is not practical as a negative working emulsion because it causes development inhibition and cannot obtain sufficient sensitivity.

Further, a positive type (internal latent image type) silver halide grain having a plurality of coating layers by halogen substitution on the outside of the inner core is known, and US Pat. Nos. 2,592,250 and 4,075,020 are known.
The details are described in Japanese Patent Publication No. 55-127549. These silver halide grains are often used in an internal latent image type direct positive photosensitive material for diffusion transfer and the like, which naturally has too high an internal sensitivity.
It is not used at all in the negative emulsion targeted by the present invention.

On the other hand, JP-A-58-181037, JP-A-60-35726, JP-A-59-116647, etc. each have an outer shell on the inner core as described above and each layer contains iodine. Silver halide grains with various amounts taken into consideration are shown.

In the field of silver halide photographic light-sensitive materials, color sensitive materials having an ISO display sensitivity of more than 1000 have recently appeared due to various technological advances. However, as the sensitivity of these sensitive materials increases, the graininess and sharpness usually deteriorate, and the image quality is inferior to that of the conventional sensitive materials, which makes them unattractive for consumers. At present, it is unsatisfactory, and a high-sensitivity negative photosensitive material having excellent graininess and sharpness is desired.

In astrophotography, indoor photography, sports photography and the like, negative photosensitive materials having higher sensitivity are required.

On the other hand, the following techniques are known as techniques for increasing the sensitivity. For example, a red light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer and a blue light-sensitive silver halide emulsion layer (hereinafter referred to simply as "emulsion") Layer)), a high-sensitivity silver halide emulsion layer (hereinafter referred to as a high-sensitivity emulsion) containing a diffusion-resistant coupler that develops substantially the same hue with respect to some or all of the photosensitive emulsion layers. Layer) and a low-sensitivity silver halide emulsion layer (hereinafter referred to as a low-sensitivity emulsion layer) are known to have the same color-sensitive silver halide emulsion layer as a separate multilayer structure. For example, not only the emulsion layer on the side closer to the support is absorbed by the other emulsion layers on the side farther on exposure, but it also takes time for the developer to diffuse during development. There was a problem of this. That is, in such a forward layer structure, it was difficult to achieve high sensitivity for the green-sensitive and red-sensitive emulsion layers located in the lower layers due to the loss of the exposure amount and the delay of the development.

On the other hand, a technique of changing the layer order of each emulsion layer is known.

For example, in U.S. Pat.No. 3,663,228, (a) a red-sensitive, green-sensitive, and blue-sensitive low-sensitivity emulsion layer is coated on the side closer to the support, and (b) the support. It is known that a red-sensitive, green-sensitive and blue-sensitive high-sensitivity emulsion layer is coated in this order from the support on the side farther from the body. This technique provides higher sensitivity than the light-sensitive material having the normal layer structure, but each unit of the high-sensitivity emulsion layer and the low-sensitivity emulsion layer is N
As is clear from the fact that they are separated by the D (neutral density) filter, the enhancement of sensitivity was not a problem of the inventor.

Next, U.S. Pat. No. 3,658,536 discloses that a green-sensitive emulsion layer, which has a great influence on luminosity, is provided on a surface farther from a support, as shown in FIG. 5 of the drawings attached to the specification. By locating it on the side, a technique for eliminating the exposure loss of the layer is disclosed, but there is no mention of a technique for increasing the sensitivity of the blue-sensitive emulsion layer,
Moreover, the improvement of sharpness and graininess was insufficient.

For other techniques related to changing the layer structure, see
Nos. 51-49027, 53-97424 and U.S. Pat.
The technology and the like described in the specification of No. 446 are known. But,
These are all higher in sensitivity than the light-sensitive material of the normal layer constitution, but not only the sensitivity of the green-sensitive and red-sensitive emulsion layers is insufficient, but also the effect of improving image quality such as graininess and sharpness. Was not enough.

C. OBJECT OF THE INVENTION An object of the present invention is to provide a negative-working silver halide photographic light-sensitive material having high sensitivity, excellent sensitivity-fogging relationship, wide exposure area, and excellent graininess and sharpness.

D. Structure of the Invention and Effects of the Invention That is, the present invention has blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers, and at least one of these silver halide emulsion layers has different sensitivities. It is composed of a plurality of layers, and the plurality of layers are composed of a low-sensitivity layer and a high-sensitivity layer which are sequentially arranged when viewed from the support side, and at least one silver halide emulsion layer having different color sensitivity is provided between these layers. A photographic light-sensitive material which is provided with at least one high-sensitivity layer of at least one silver halide emulsion layer, and an internal core consisting essentially of silver bromide and / or silver iodobromide, Negative silver halide grains provided outside the nucleus and having a plurality of outer shells substantially composed of silver bromide and / or silver iodobromide are contained, and the outermost silver halide grains are contained. Iodine content of shell is 10 mol% or less And a, and than iodine content of the outermost shell 6
The present invention relates to a silver halide photographic light-sensitive material characterized in that a shell having a high iodine content of more than mol% is provided inside the outermost shell.

In the silver halide composition of the silver halide grains according to the present invention, the above-mentioned "consisting essentially of ..." means a halogen other than silver bromide or silver iodobromide as long as the effect of the present invention is not impaired. It means that it may contain silver chloride, for example, silver chloride. Specifically, in the case of silver chloride, the ratio is 1 mol%.
The following is desirable.

Summarizing the features of the photographic light-sensitive material according to the present invention,
It is like (1) to (8) below.

(1) By using an emulsion containing core / shell type silver halide grains having a high iodine shell inside, high sensitivity (a wide range of exposure) and excellent graininess (compared to non-core / shell emulsions) can be obtained. can get.

(2) By providing an intermediate shell having an intermediate iodine content between the high iodine shell and the surface low iodine shell (outermost shell layer), higher sensitivity can be obtained.

(3) The iodine content of the high-iodity shell is preferably 6 to 40 mol% and is higher than the outermost shell layer by 6 mol% or more, but when this content is less than 6 mol% (or the outermost shell layer). If the amount is less than 6 mol%), the sensitivity decreases, and if it exceeds 40 mol%, polydispersion occurs, and it is preferable that the amount does not exceed 40 mol% from the viewpoint of sensitivity and sharpness.

(4) The difference in iodine content between the middle shell and the outermost shell or the high iodine shell is preferably 3 mol% or more. This is because if the difference is too small, the effect of the intermediate shell decreases (sensitivity decreases). The difference in iodine content is 35 mol%
The upper limit is desirable from the viewpoint of effectively drawing out the effect of the intermediate shell (sensitivity, monodispersity, fog-sensitivity relationship, sharpness).

(5) If the iodine content in the entire silver halide grains is too high, the developability will be poor and the sensitivity will be reduced.If it is too low, the gradation will be too hard, the exposure area will be narrow, and the graininess will be poor. Since there is a tendency for deterioration of the properties, it is preferable to select a specific range.

(6) The monodisperse emulsion is superior to the polydisperse emulsion in sensitivity, sharpness and fog-sensitivity relationship. That is, in polydispersion, the reaction of forming a shell is non-uniform, so that it is difficult to form an ideal core / shell structure, the presence of fine particles that deteriorate the sharpness, and chemical sensitization after particle formation. Since the optimum conditions differ depending on the individual grains, the sensitivity is low and the fog-sensitivity relationship tends to be poor, and a monodisperse emulsion is preferably used.

(7) In a multi-layer color light-sensitive material, a phenomenon in which the sensitivity is deteriorated due to multi-layering is called as compared with the case of a single layer (called a multi-layer desensitizing effect). In addition to being high, the multilayer desensitization effect is less likely to occur, and the multi-layer color light-sensitive material can be used more effectively.

(8) According to the layer structure of the photographic light-sensitive material of the present invention, high sensitivity can be achieved and excellent sharpness and graininess can be achieved. This will be described later.

In order to further improve the above-mentioned excellent effects, I _h : iodine content (mol%) of high iodine shell I _m : iodine content (mol%) of intermediate shell I _l : iodine content of outermost shell (Mol%), ΔI = I _h −I> 8 mol%, ΔI _h = I _h
-I _m > 4 mol%, ΔI _l = I _m −I _l > 4 mol%, ΔI> 10 mol%, ΔI _h > 4 mol%, ΔI
_It is even better to have _l > 4 mol% (supra). here,
I ₁ = 0 to 5 mol%, preferably 0 to 2 mol%, and more preferably 0 to 1 mol%. Also, I _h is 6
-40 mol% is preferable, and 10-40 mol% is more preferable (described above).

Also, the volume of the outermost shell is preferably 4 to 70 mol% of the whole particle,
10 to 50 mol% is more preferable. The volume of the high-iodity shell is preferably 10 to 80% of the total grains, 20 to 50%, and further
20-45% is desirable. The volume of the intermediate shell is 5 to 5
60%, more preferably 20-55%. The high-iodity shell may be at least a part of the inner shell, but it is preferable that the inner core exists separately inside the high-iodity shell.

The iodine content of the inner core is preferably 0 to 40 mol%, preferably 0 to 10 mol%, more preferably 0 to 6 mol%. The particle size of the inner core is preferably 0.05 to 0.8 μm, more preferably 0.05 to 0.4 μm.

Further, in the above-mentioned characteristic point, the iodine content in the whole grain is preferably 1 to 20 mol%, preferably 1 to 15 mol%, and more preferably 2 to 12 mol%. At the above-mentioned characteristic points, the particle size distribution of the particles is polydisperse,
Either monodisperse is acceptable, but the coefficient of variation of particle size distribution is 20%
The following monodisperse emulsions are recommended, and the same coefficient of variation
It should be 15% or less. This coefficient of variation is Is a measure of monodispersity.

The grain size of silver halide grains (defined as the length of one side of a cube having the same volume as the silver halide grains) is preferably 0.1 to 3.0 μm. The shape may be any of an octahedron, a cube, a sphere and a flat plate, but an octahedron is preferable.

The layer structure of the silver halide grain of the present invention will be further described. The inner core and the high-iodine shell may be the same as described above, or a separate inner core is provided inside the high-iodine shell. May be. The inner core and the high-iodity shell, the high-iodity shell and the intermediate shell, the intermediate shell and the outermost shell may be adjacent to each other, or at least one layer of another shell having an arbitrary composition between the shells. (May be referred to as an arbitrary shell).

These arbitrary shells may be a single shell having a uniform composition, may be a group of shells composed of a plurality of shells having a uniform composition, and have a composition that changes stepwise, or may be continuous in an arbitrary shell. It may be a continuous shell having a composition that changes with time, or a combination thereof. Further, there may be a plurality of high-iodity shells and intermediate shells, or only one set.

Next, an example of the layer structure of silver halide grains according to the present invention will be described. The iodine content is shown as 1.

1. Inner core = 3-layer structure of high-iodity shell Iodine content Shell diameter Core (3rd) (Inner core = high-iodity shell) I ₃ -I ₂ > 3 mol% I ₃ = 15 mol% 1.2 μm Second shell (Intermediate shell) I ₂ −I ₁ > 3 mol% I ₂ = 5 mol% 1.4 μm First shell (outer shell) I ₁ = 0 to 10 mol% I ₁ = 0.5 mol% 1.6 μm 2. Six-layer structure including fourth and fifth shells of arbitrary composition between the inner core and the high iodine shell Iodine content Shell diameter Core (sixth) (inner core) Optional I ₆ = 4.0 mol% 0.1 μm 5 shell (-) option I ₅ = 2.0 mol% 0.27 μm 4 th shell (-) option I ₄ = 2.6 mol% 0.8 μm 3rd shell (high iodine shell) I ₃ -I ₂ > 3 mol% I ₃ = 15.0 mol% 1.12 μm Second shell (intermediate shell) I ₂ −I ₁ > 3 mol% I ₂ = 5.0 mol% 1.44 μm First shell (outer shell) I ₁ = 0 to 10 mol% I ₁ = 0.5 mol% 1.6 μm 3. 7-layer structure with optional 5th and 6th shells between the inner core and the high iodine shell, and 2 intermediate shells between the outermost shell and the high iodine shell Iodine content Shell diameter 7th shell ( Inner core) I ₇ = 4 mol% 0.10 μm 6th shell (arbitrary insertion shell) Optional I ₆ = 2 mol% 0.27 μm 5th shell (arbitrary insertion shell) Optional I ₅ = 8 mol% 0.8 μm 4 shells (high iodine shell) I ₄ -I ₃ > 3 mol% I ₄ = 15 mol% 1.12 μm 3rd shell (intermediate shell) Second shell (intermediate shell) First shell (outermost shell) I ₁ = 0 to 10 mol% I ₁ = 0.5 mol% 1.6 μm 4. Any 6th and 7th shell between the inner core and the high-iodity shell, and 1 layer of arbitrary shell (4th shell) between the high-iodity shell (5th shell) and the intermediate shell (3rd shell) , And an eight-layer structure with one layer of arbitrary shell (second shell) between the middle shell (third shell) and the outermost shell Iodine content rate Shell diameter Eighth shell (inner core) Optional I ₈ = 4 mol % 0.10 μm 7th shell (arbitrary shell) Optional I ₇ = 2 mol% 0.27 μm 6th shell (arbitrary shell) Optional I ₆ = 4 mol% 0.8 μm 5th shell (high iodine shell) I ₅ -I _3> 3 mole% _{I 5} = 15 mol% 1.12 .mu.m fourth shell (optional shell) arbitrary I ₄ = 9 mol% 1.24 .mu.m third shells (intermediate shell) _I 3 _-I 1 = 3 mole% _I 3 = 5 Mol% 1.44μm 2nd shell (arbitrary shell) Optional I ₂ = 4.5mol% 1.50μ
m 1st shell (outermost shell) I ₁ = 0 to 10 mol% I ₁ = 2 mol% 1.6 μm 5 Structure having a plurality of high iodine shells Iodine content ratio Shell diameter 6th shell (inner core) Optional I ₆ = 4 mol% 0.10 μm 5th shell (high iodine shell) I ₅ −I ₂ > 3 mol% I ₅ = 15 mol% 0.27 μm I ₅ −I ₁ > 6 mol% 4th shell (arbitrary shell) Meaning I ₄ = 5 mol% 0.80 μm Third shell (high iodine shell) I ₃ −I ₂ > 3 mol% I ₃ = 15 mol% 1.12 μm I ₃ −I ₁ > 6 mol% Second shell (intermediate shell) ) I ₂ -I ₁ > 3 mol% I ₂ = 5 mol% 1.44 μm First shell (outermost shell) I ₁ = 0 to 10 mol% I ₁ = 0.3 mol% 1.60 μm of the silver halide grains of the present invention. The inner core is written by P. Glafkides, Chimie et Physique. Photohraphique (Paul Montel, 1967), G. F. Danfin (GFDuffin) Author photo graphic-Imarujon chemistry (Photographic Emulsion Chimistry)
(Published by The Focal Press, 1966
), VL Zelikman et al. Making and coating photography
Imaging (Making and Coating Photographic Emuls
ion) (published by The Focal Press, 1
964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a form of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used. Good.

It is also possible to use a method in which grains are formed in the presence of excess silver ions (so-called reverse mixing method). PA in the liquid phase where silver halide is produced as one of the simultaneous mixing methods
It is also possible to use a method of keeping g constant, that is, a so-called controlled double jet method. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used, but it is preferable to use the double jet method or the control double jet method.

The pAg at the time of preparing the internal core varies depending on the reaction temperature and the kind of the silver halide solvent, but it is preferably 2 to 11. Further, it is preferable to use a silver halide solvent because the grain formation time can be shortened. For example, a commonly known silver halide solvent such as ammonia or thioether can be used.

The shape of the inner core may be a plate, a sphere, a twin system, or may be an octahedron, a cube, a tetradecahedron, or a mixed system.

In addition, in order to make the particle size uniform, British Patent 1,535,01
No. 6, JP-B-48-36890 and JP-B No. 52-16364, a method of changing the addition rate of an aqueous solution of silver nitrate or an alkali halide according to the grain growth rate, and US Pat.
As described in JP-A No. 4,242,445 and JP-A No. 55-158124, it is preferable to grow rapidly within a range not exceeding the critical saturation by using a method of changing the concentration of the aqueous solution.
In these methods, re-nucleation does not occur and each silver halide grain is uniformly coated, so that an arbitrary shell, a high iodine shell,
It is also preferably used when introducing the middle shell and the outermost shell.

If desired, a single or a plurality of arbitrary shells can be provided between the high iodine shell and the inner shell of the silver halide grain of the present invention. This high iodine shell can be provided by a normal halogen substitution method, a method of coating with a silver halide, etc. after a desalting step is optionally performed on the formed internal core or the internal shell provided with an arbitrary shell.

The halogen substitution method can be carried out, for example, by adding an aqueous solution mainly containing an iodo compound (preferably iodine potassium) after the inner core is formed, preferably an aqueous solution having a concentration of 10% or less. Specifically, it can be carried out by the method described in U.S. Pat. Nos. 2,592,250, 4,075,020, JP-A-55-127549, and the like. At this time, in order to reduce the difference in iodine distribution between the grains of the high iodine shell, it is desirable to adjust the concentration of the aqueous iodine compound solution to 10 ^-2 mol% or less and to add it for 10 minutes or more.

As a method for newly coating the inner core with silver halide, for example, simultaneous addition of a halide aqueous solution and a silver nitrate aqueous solution, that is, a simultaneous mixing method or a control double jet method can be performed. Details are described in JP-A-53-22408, JP-B-43-13162, JP-A-58-14829, J. Photo Science (J. Photo.Sci.), 24, 198 (1976), etc. Can be done by the method described.

The pAg at the time of forming the high-iodine shell is the reaction temperature,
Although it varies depending on the kind and amount of the silver halide solvent, those described above are preferably used in the same manner. When ammonia is used as the solvent, it is preferably 7-11.

As a method of forming a high-iodity shell, a simultaneous mixing method or
The control double jet method is more preferable.

The intermediate shell of the silver halide grain of the present invention has a high-iodity shell on the surface or, if necessary, a single or a plurality of arbitrary shells on the high-iodity shell, an internal core. Can be further provided on the outside of the grains containing silver by a method of coating a silver halide having a halogen composition different from the halogen composition of the high iodine shell by a simultaneous mixing method or a control double jet method.

As for these methods, the above-mentioned method of providing the high-iodity shell is similarly used.

The outermost shell of the silver halide grain of the present invention is an intermediate shell having an intermediate shell on its surface, or optionally having one or more arbitrary shells on the intermediate shell, a high iodine shell, an internal shell. Can be provided on the outer side of the grains containing a silver halide having a halogen composition different from the halogen composition of the high iodine shell by a simultaneous mixing method or a control double jet method.

As for these methods, the method of providing the above-mentioned high-iodity shell is similarly used.

As the optional shell, one layer or a plurality of layers may be provided between the inner shell and the high-iodity shell, between the high-iodity shell and the intermediate shell, and between the intermediate shell and the outermost shell, if necessary. good. As for these arbitrary shells, the method of providing the above-mentioned high-iodity shell is similarly used. The inner shell, the high-iodity shell, the intermediate shell, the outermost shell, and the optional shell at each position may be subjected to a desalting step according to a conventional method, if necessary, during the process of providing adjacent shells, or desalting. You may form a shell continuously, without performing a process.

The iodine content of each coating shell of the silver halide grain of the present invention is described in, for example, J. I. Goldstein
ln), D.I. B. Williams "TEM / AT
X-ray analysis in EM "Scanning Electron Microscopy (1977), Volume 1 (IIT Research
It can also be determined by the method described in Institute, page 651 (March 1977).

The silver halide grain as the final product after forming the outermost shell of the present invention is an excess halogen compound produced at the time of preparation, or salts of by-produced or unnecessary nitrates, ammonia and the like, compounds are a dispersion medium of the grain. May be removed from.
The removal method is a Nudel water washing method, a dialysis method, or an inorganic salt, an anionic surfactant, an anionic polymer (for example, polystyrene sulfonic acid), or a gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.) commonly used in general emulsions. The precipitation method utilizing), the pseudoprecipitation (flocculation) method and the like can be appropriately used.

The core / shell type silver halide grain of the present invention can be optically sensitized in a desired wavelength range. There is no particular limitation on the optical sensitization method, and for example, a cyanine dye such as a zeromethine dye, a monomethine dye, a dimethine dye, a trimethine dye or an optical sensitizer such as a merocyanine dye may be used alone or in combination to optically sensitize. can do. Combinations of sensitizing dyes are often used especially for the purpose of supersensitization.
A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light, together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. For these technologies, U.S. Patents 2,688,545 and 2,912,329,
3,397,060, 3,615,635, 3,628,964, British Patents 1,195,302, 1,242,588, 1,293,862, West German Patent (OLS) 2,030,326, 2,121,780, Japanese Patent Publication
43-4936, 44-14030, Research Disclosure, Vol. 176, 17643 (issued in December 1978), page 23, Item IV, etc. The selection can be arbitrarily determined depending on the wavelength region to be sensitized, sensitivity, etc., according to the purpose and application of the light-sensitive material.

The core / shell type silver halide crystal of the present invention can be subjected to various chemical sensitization methods applied to general emulsions.

For chemical sensitization, H. Friesew edited by Die Grundtragen der Photokraischen Prozesemit Silber Harlogeneden (Die
Grundlagen der Photographische Prozesse mit Silbe
rhalogeniden) (Akademische Verlagsgesellschaft), 1968) 6
The method described on pages 75 to 734 can be used. That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are U.S. Pat.Nos. 1,574,944, 2,410,689, 2,
278,947, 2,728,668, 3,656,955, 4,032,928,
4,067,740. Examples of the reduction sensitizers include primary tin salts, amines, hydrazine derivatives, formamidinesulfinic acid, and silane compounds, and specific examples thereof are U.S. Pat.No. 2,487,850, 2,419,974.
No., 2,518,698, 2,983,609, 2,983,610, 2,694,6
37, 3,930,867, 4,054,458. For sensitizing precious metals, in addition to gold complex salts, platinum, iridium,
A complex salt of a metal of Group VIII of the periodic table such as palladium can be used, and specific examples thereof are U.S. Patents 2,399,083 and 2,448,0.
No. 60, British Patent 618,061 and the like.

The silver salt grains of the present invention can use a combination of two or more of these chemical sensitization methods.

The amount of coated silver is arbitrary, but preferably 1000 mg / m ² or more,
15000 mg / m ² or less, more preferably 2000 mg / m ²
As described above, it is 10000 mg / m ² or less.

Further, the photosensitive layer containing the particles may be present on both sides of the support.

When forming each shell of the core / shell type emulsion of the present invention, various dopants can be doped. Examples of the internal dopant include silver, ions, iridium,
It includes gold, platinum, osmium, rhodium, tellurium, selenium, cadmium, zinc, lead, thallium, iron, antimony, bismuth, arsenic and the like.

In order to dope these dopants, each water-soluble salt or complex salt can coexist when forming each shell.

It is extremely important that the core / shell type silver halide grains described above are contained in at least one high-sensitivity emulsion layer.

In a preferred embodiment of the present invention, (1) the layer containing the core / shell type silver iodobromide grains of the present invention is at least a high-sensitivity blue-sensitive emulsion layer and / or a high-sensitivity green-sensitive emulsion layer and / or a high-sensitivity red. It is a sensitive emulsion layer, and particularly preferably,
It is a green-sensitive and / or red-sensitive emulsion layer. (2) As the light-sensitive emulsion layer of the light-sensitive material of the present invention, from the side closer to the support, red-sensitive, green-sensitive and blue-sensitive low-sensitivity emulsion layers are coated, and thereon. That is, each of high-sensitivity emulsion layers of red-sensitivity, green-sensitivity and blue-sensitivity is coated.

The high-sensitivity emulsion layer and the low-sensitivity emulsion layer have substantially the same color sensitivity, and after the color development processing,
The two emulsion layers preferably contain a photographic diffusion-resistant coupler capable of forming a color forming dye having substantially the same hue.

Between the low-sensitivity layer and the high-sensitivity layer of the blue-sensitive emulsion layer in the present invention, at least one red-sensitive and green-sensitive emulsion layer (hereinafter referred to as red-sensitive emulsion layer and green-sensitive emulsion layer) are provided. Although provided, it is preferable that the green-sensitive emulsion layer is located farther from the support than the red-sensitive emulsion layer. With such a constitution, it is possible to reduce the influence of light scattering by the silver halide grains contained in the layer above the green-sensitive emulsion layer, which has a great influence on the visibility.

The green-sensitive and red-sensitive emulsion layers may be separately coated in two or more layers, and the blue-sensitive and low-sensitive emulsion layers may be separately coated in two or more layers. Emulsion layers having the same color sensitivity which are separately coated as described above do not necessarily have to be adjacent to each other. Further, in the case of separately coating as described above, the respective photosensitive emulsion layers may have different sensitivities between emulsion layers having the same color sensitivity. That is, when two or more separate coatings are provided for at least one of the high-sensitivity blue-sensitive emulsion layer and the green-sensitive and red-sensitive emulsion layers, they may be divided into, for example, a high-sensitivity layer and a medium-sensitivity layer.

A low-sensitivity red-sensitive emulsion layer and a low-sensitivity green-sensitive emulsion layer may be provided closer to the support than the low-sensitivity blue-sensitive emulsion layer. In this case, the red-sensitive and green-sensitive emulsion layers are preferably high-sensitivity layers. When the low-sensitivity red-sensitive and green-sensitive emulsion layers are provided, it is preferable that the green-sensitive emulsion layer is located farther from the support than the red-sensitive emulsion layer. The low-sensitivity red-sensitive and green-sensitive emulsion layers are each 2
The above layers may be separately coated, and in this case, the sensitivity may be different between emulsion layers having the same color sensitivity. That is, when at least one of the low-sensitivity red-sensitive and green-sensitive emulsion layers is separately coated in two or more layers, for example, the medium-sensitive layer and the low-sensitive layer may be separated. These separated layers need not be adjacent between emulsion layers of the same color sensitivity.

In the light-sensitive material of the present invention, a non-photosensitive intermediate layer may be provided between the photosensitive emulsion layers, and in particular, when a photosensitive emulsion layer having a different color sensitivity is adjacent, a non-photosensitive intermediate layer is provided. preferable. Further, even when adjacent photosensitive emulsion layers are high-sensitivity layers, it is preferable to provide a non-photosensitive intermediate layer. A scavenger substance may be contained in such a non-photosensitive intermediate layer.

Although not necessary in the present invention, provision of the yellow filter layer cannot be prevented. In that case, it is preferable to provide it directly under the blue-sensitive high-sensitivity and / or low-sensitivity emulsion layer, but more preferably it is located closer to the support than the low-sensitivity blue-sensitivity emulsion layer.

Specific examples of the layer constitution of the photosensitive emulsion layer in the light-sensitive material of the present invention are shown below, but the invention is not limited thereto. The side closer to the support is mentioned first.

(1) Support, low sensitivity red-sensitive, green-sensitive and blue-sensitive emulsion layers, high-sensitivity red-sensitive, green-sensitive and blue-sensitive emulsion layers.

(2) The layer structure of (1) above, in which the medium-speed green-sensitive emulsion layer is located between the high-speed red-sensitive emulsion layer and the high-speed green-sensitive emulsion layer.

(3) The layer structure of the above (1) is different only in that the high-sensitivity red-sensitive and green-sensitive emulsion layers are vertically inverted.

(4) In the layer structure of (1) above, the low-sensitivity green-sensitive emulsion layer is separated into two layers, and a low-sensitivity and medium-sensitivity green-sensitive emulsion layer is formed from the side closer to the support.

(5) In the layer structure of (1) above, between the low-sensitivity blue-sensitive emulsion layer and the high-sensitivity red-sensitive emulsion layer, from the side close to the support, each medium-sensitivity red-sensitive and green-sensitive emulsion layer. Is located.

(6) In the layer structure of (1) above, between the low-sensitivity blue-sensitive emulsion layer and the high-sensitivity red-sensitive emulsion layer, from the side close to the support, each medium-sensitivity red-sensitivity, green-sensitivity and blue A structure in which the sensitive emulsion layer is located.

(7) In the layer structure of (1) above, each of the high-sensitivity red sensitivities,
A structure in which each of the green-sensitive and blue-sensitive emulsion layers is separated into two layers, and from the side closer to the support, the emulsion layers are defined as medium and high sensitivity emulsion layers.

(8) In the layer structure of (1) above, each of the high-sensitivity red-sensitive and green-sensitive emulsion layers is separated into two layers, and from the side close to the support, medium sensitivity and The structure is considered as a high-sensitivity emulsion layer.

(9) The layer structure of (1) above, in which the middle-speed blue-sensitive emulsion layer is located between the low-speed blue-sensitive emulsion layer and the high-speed red-sensitive emulsion layer.

(10) In the layer structure of (1) above, each of the low-sensitivity red-sensitive and green-sensitive emulsion layers is separated into two layers, and from the side close to the support, the low-sensitivity and medium-sensitivity of each emulsion layer. A structure that is used as an emulsion layer.

(11) In the layer structure of (1) above, each of the low-sensitivity red-sensitive, green-sensitive and blue-sensitive emulsion layers is separated into two layers, and each emulsion layer has low sensitivity from the side close to the support. And a structure having a medium-speed emulsion layer.

(12) In the layer structure of (1) above, the low-sensitivity red-sensitive emulsion layer is separated into two layers, and a low-sensitivity and middle-sensitivity red-sensitive emulsion layer is formed from the side closer to the support.

The specific examples of the layer constitution of the photosensitive emulsion layer in the light-sensitive material of the present invention have been described above. Of course, other constituent layers such as

Although the grain size of the photosensitive silver halide used in the photosensitive emulsion layer of the present invention is not limited, for example, in the case of the high-sensitivity emulsion layer, in order to reduce the sharpness deterioration of the emulsion layer located below, It is preferable to avoid the presence of small particles with large light scattering, and it is preferable that the average particle diameter is 0.7 to 2.5 μm. Further, it is preferable that the medium-speed emulsion layer has a thickness of 0.5 to 1.5 μm and the low-speed emulsion layer has a thickness of 0.2 to 1.0 μm.

In the light-sensitive material of the present invention, it is not necessary to include a scavenger substance which is an oxidized product of a developing agent, but it does not prevent inclusion in a non-photosensitive intermediate layer or other photographic constituent layers. Any type of scavenger substance that reacts with the oxidized product of the developing agent to deactivate it can be used. Documents regarding these scavengers include, for example, U.S. Patent Nos. 2,336,327, 2,360,290, and
No. 2,403,721, No. 2,701,197, No. 2,710,801, No. 2,728,659, No. 3,718,464 and the like can be mentioned, and among the scavenging substances described in these documents, particularly colorless ones can be preferably used.

As a binder for the core / shell type silver halide grains according to the present invention or a dispersion medium used for producing them, a hydrophilic colloid usually used in silver halide emulsions is used. As the hydrophilic colloid, not only gelatin (which may be lime-treated or acid-treated) but also gelatin derivatives such as gelatin and aromatic sulfonyl chloride, acid chloride, as described in US Pat. No. 2,614,928,
Gelatin derivatives made by reaction with acid anhydrides, isocyanates, 1,4-diketones, US Pat. No. 3,118,766
Derivatives made by reacting gelatin with trimellitic anhydride as described in Japanese Patent Publication No. 39-5514
No. 3,186,846.Gelatin derivatives obtained by reaction of an organic acid having an active halogen and gelatin described in JP-B No. 42-26845, gelatin derivatives obtained by reaction of aromatic glycidyl ether with gelatin described in JP-B No. 42-26845, and U.S. Pat. Maleimide, maleamic acid, gelatin derivative by reaction with unsaturated aliphatic diamide, etc., gelatin, sulfoalkylated gelatin described in British Patent 1,033,189, polyoxyalkylene derivative of gelatin described in US Pat. No. 3,312,553, etc. A high molecular weight grafted product of gelatin such as acrylic acid, methacrylic acid, esters thereof with monohydric or polyhydric alcohols, amides, acrylic (or methacrylic) ethryl, styrene and other vinyl monomers alone or in combination. Grafted on gelatin; synthetic Hydrophilic polymeric substances,
For example, homopolymers containing monomers such as vinyl alcohol, N-vinylpyrrolidone, hydroxyalkyl (meth) acrylate, (meth) acrylamide, N-substituted (meth) acrylamide, etc. or copolymers thereof, and (meth ) Acrylic esters, vinyl acetate, copolymers with styrene, etc., copolymers of any of the above with maleic anhydride, maleamic acid, etc .; natural hydrophilic polymer substances other than gelatin, such as casein,
Agar, alkyne acid polysaccharides and the like can be used alone or in combination.

The silver halide photographic emulsion containing the core / shell type silver halide grains according to the present invention can contain various additives usually used depending on the purpose. Examples of these additives include azoles or imidazoles, such as benzothiazolium salts, nitroinsoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles; triazoles such as aminotriazoles, benzotriazoles, nitrobenzotriazoles; tetrazoles such as mercaptotetrazole (especially 1-phenyl-5
-Mercaptotetrazole); mercaptopyrimidines; mercaptotriazines, for example thioketo compounds such as oxazolithione; azaindenes, for example triazaindenes, tetraazaindenes (especially 4
-Hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc .; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, imidazolium salt, tetrazolium salt, polyhydroxy compound, etc. Stabilizers and antifoggants can be included.

The photographic light-sensitive material using the core / shell type emulsion of the present invention may contain an infinite or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-S-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-S-). Triazine, etc.), mucohalogenates (mucochloric acid, mucophenoxycyclo acid, etc.). Etc. can be used alone or in combination.

The photographic sensitizer using the core / shell type emulsion of the present invention includes
The photographic emulsion layer and other hydrophilic colloid layers may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination with methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalk (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

The silver halide photographic light-sensitive material according to the present invention contains, if necessary, a development accelerator such as benzyl alcohol or polyoxyethylene compound; a chroman-based, Claman-based, bisphenol-based or phosphite-based image stabilizer; wax,
It may contain a lubricant such as glyceride of a higher fatty acid, a higher alcohol ester of a higher fatty acid, a development modifier, a developing agent, a plasticizer, and a bleaching agent. A coating aid as a surfactant that may be contained, an agent for improving the permeability to a treatment liquid, etc.,
As an antifoaming agent or a material for controlling various physical properties of the light-sensitive material, various kinds of anionic type, cationic type, nonionic type or amphoteric type can be used. As the antistatic agent, diacetyl cellulose, a styrene perfluoroalkyl sodium sulphate maleate copolymer, an alkali salt of a reaction product of a styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, and the like are effective. Examples of matting agents include methyl polymethacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Examples of the latex added to improve the physical properties of the film include copolymers of acrylic acid ester, vinyl ester and the like with other monomers having an ethylene group. Examples of the gelatin plasticizer include glycerin and glycol compounds, and examples of the thickener include styrene-sodium maleate copolymer and alkyl vinyl ether-maleic acid copolymer.

The emulsion having silver halide grains of the present invention can have a rich latitude by mixing at least two types of emulsions having different average grain sizes but different sensitivities or by performing multi-layer coating.

The mixed silver salt crystal according to the present invention is used for general black and white, X ray,
Effectively applied to photographic light-sensitive materials for various purposes such as color, infrared, micro, silver dye bleaching, reversal, diffusion transfer, high contrast, photothermography, and photothermographic material. However, it is particularly suitable for a color sensitive material having high sensitivity.

To apply the core / shell type silver halide emulsion according to the present invention to a photographic light-sensitive material for color, an emulsion containing the above-mentioned crystals of the present invention adjusted to have a red-sensitivity, a green-sensitivity and a blue-sensitivity is used. The method and material used for the color light-sensitive material may be applied, such as the combination of a yellow coupler. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (such as benzoylacetanilides, Baroyl acetanilides) and the like, and cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, it may be a colored coupler having a color correcting effect, or a coupler (so-called DIR coupler) which releases a development inhibitor upon development. In addition to the DIR coupler, a non-colored DI in which the product of the coupling reaction is colorless and releases a development inhibitor.
R coupling may be included.

In carrying out the present invention, the following known anti-fading agents can be used in combination, and the color image stabilizers used in the present invention can be used alone or in combination of two or more kinds. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols.

The light-sensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used. These UV absorbers may be fixed in the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

The light-sensitive material of the present invention includes a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative as an antifoggant,
You may contain an ascorbic acid derivative etc.

The present invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support.
The order of these layers can be arbitrarily selected as required. It is usual to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods, such as tape coating method, roller coating method and curtain coating method. A coating method, an extrusion coating method, or the like can be used. U.S. Patents 2,681,294 and 2,7
The methods described in 61,791 and 3,526,528 are advantageous methods.

As the support of the photographic light-sensitive material, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass, cellulose acetate, cellulose nitrate,
Polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, and commonly used materials such as polystyrene can be appropriately selected according to the intended use of each photographic light-sensitive material.

These supports are subjected to a subbing process, if necessary.

The photographic sensitizer having the core / shear type silver halide emulsion according to the present invention can be developed after exposure by a known method usually used.

The black-and-white developing solution is an alkaline solution containing a developing agent such as hydroxybenzenes, aminophenols, aminobenzenes, and other alkali metal sulfites, carbonates,
It may contain bisulfite, bromide, iodide and the like. Further, when the photographic light-sensitive material is for color, color development can be carried out by a commonly used color development method. In the reversal method, first, development is carried out with a black-and-white negative developing solution, then white exposure is carried out or processing is carried out in a bath containing a fogging agent, and then color development is carried out with an alkaline developing solution containing a color developing agent.
There is no particular limitation on the treatment method, and any treatment method can be applied, for example, as a typical one,
After color development, apply bleach-fixing treatment, and then wash and stabilize treatment if necessary, or after color development, apply bleaching and fixing treatment separately, and then wash and stabilize treatment as needed. You can The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known general aromatic amine developers such as phenylenediamines (eg 4-amino-N, N).
-Diethylaniline, 3-methyl-4-amino-N, N
-Diethylaniline, 4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfoamidoethylaniline, 4-amino-3-methyl-
N-ethyl-N-β-methoxyethylaniline, etc.)
Can be used.

Elsewhere, LFA Mason's Photographic Processing Chemistry (Photogr
aphic Processing Chemistry) Focal Press (Foca
Press), 1966), pages 226-229, U.S. Patent 2,193,01.
Nos. 5, 2,592,364 and JP-A-48-64933 may be used.

The color developing solution may further contain a pH buffering agent development inhibitor or antifoggant. Also, if necessary,
It may contain a water softener, a preservative, an organic solvent, a development accelerator, a dye-forming coupler, a competitive coupler, a fogging agent, an auxiliary developing agent, a tackifier, a polycarboxylic acid type chelating agent, an antioxidant and the like.

The photographic emulsion layer after color development is usually bleached. The bleaching treatment may be carried out at the same time as the fixing treatment, or as a bleaching agent which may be carried out individually, iron (III), cobalt (I
V), chromium (VI), polyvalent metal compounds such as copper (II), peracids, quinones, nitroso compounds, etc. are used.

For bleaching or bleach-fixing solutions, U.S. Pat.
Various additives can be added in addition to the bleaching accelerators described in 3,241,966, JP-B-45-8506, JP-B-45-8836 and the thiol compounds described in JP-A-53-65732.

Next, a production example of silver halide grains according to the present invention will be specifically described.

Production Example 1 (1-1) Production of Inner Core: A silver iodobromide emulsion EM-1 containing 4 mol% of silver iodide was produced using the following 6 kinds of solutions.

(Solution A-1) Ocein gelatin 39.7 g Distilled water 3936 ml Polyisopropylene-polyethylene oxy-disuccinate sodium salt 10% ethanol solution 35.4 ml Magnesium sulfate 3.6 g 6% nitric acid 75.6
ml Potassium bromide 2.06g (Solution B-1) Ocein gelatin 35.4g Potassium bromide 807g Potassium iodide 47g Polyisopropylene-polyethylene oxy-disuccinate sodium salt 10% ethanol aqueous solution 35.4ml Distilled water 1432ml (Solution E) -1) Silver nitrate 1200g 6% nitric acid 62ml Distilled water 1467ml (Solution F-1) 25% KBr aqueous solution pAg adjustment required amount (Solution H-1) 6% nitric acid pH adjustment required amount (Solution I-1) 7% sodium carbonate aqueous solution At the required pH adjustment amount of 40 ° C., the solutions A-1 and B were added to the solution A-1 by using the mixing stirrer disclosed in JP-A-57-92523 and JP-A-57-92524.
-1 and -1 were added by the double jet method. P during simultaneous mixing
Table 1 shows the addition rates of Ag, pH and solutions E-1 and B-1.
It was controlled as shown in. The pAg and pH were controlled by changing the flow rates of the solution F-1 and the solution H-1 with a roller tube pump having a variable flow rate.

3 minutes after the addition of the solution E-1 was completed, the pH was adjusted by the solution I-1.
Was adjusted to 5.5. Next, the product was washed with desalted water by a conventional method, dispersed in an aqueous solution containing 125 g of ossein gelatin, and then the total amount was adjusted to 4800 ml with distilled water.

This emulsion has an average grain size of 0.09 μm as observed by electron microscopy.
It was found to be a monodisperse emulsion of. The particle size here is the side length when the volume of the particles is converted into a cube having the same volume, and the same applies to the following description.

(1-2) Addition of Fifth Shell: Using the following five types of solutions, EM-1 was used as a seed emulsion, and a shell of silver iodobromide having a silver iodide content of 2 mol% was added thereto. Emulsion EM-2 was prepared.

(Solution A-2) Ocein gelatin 34.54 g Distilled water 8642 ml Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% aqueous ethanol solution 20 ml 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 181.32 mg 28% ammonia water 117.4 ml 56% aqueous acetic acid solution 154 ml magnesium sulfate 16 g seed emulsion (EM-1) 0.329 mol equivalent (solution B-2) ossein gelatin 18.72 g KBr 763.8 g KI 21.8 g 4-hydroxy-6- Methyl-1,3,3a, 7-tetraazaindene 2.17 g Magnesium sulfate 7.4 g Distilled water 1578 ml (Solution E-2) AgNO ₃ 1142.4 g 28% ammonia water 931.4 ml Distilled water to make 1921 ml.

(Solution F-2) 50% KBr aqueous solution, pAg adjustment required amount (Solution G-2) 56% acetic acid aqueous solution, pH adjustment required amount At 40 ° C, the mixing stirrer disclosed in JP-A-57-92523 and 57-92524 is used. Solution A-2 is used as solution E-2 and B-
2 and 2 were added by the simultaneous mixing method for a minimum time of 32.5 minutes without the generation of small particles on the way. PAg, p during simultaneous mixing
The addition rates of H and solutions E-2 and B-2 were continuously controlled as shown in Table-2. The pAg and pH are controlled by solution F-2 and solution G by a roller tube pump with variable flow rate.
-2 and solution B-2 were changed in flow rate.

2 minutes after the addition of the solution E-2 was completed, pA was measured by the solution G-2.
g to 10.4 and after a further 2 minutes the pH is adjusted to 6 with solution F-2.
Adjusted to 0.

Next, deionized water is washed by a conventional method, and ossein gelatin is used.
After being dispersed in an aqueous solution containing 128.6 g, the total amount was adjusted to 3000 ml with distilled water.

This emulsion has an average grain size of 0.27 μm as observed by electron microscopy.
It was found to be a highly monodisperse emulsion with a coefficient of variation of grain size distribution of 12%.

(1-3) Addition of Fourth Shell: Using the following five types of solutions, the above EM-2 was used as a seed emulsion, and a shell of silver iodobromide having a silver iodide content of 2.6 mol% was provided. Emulsion EM-3 was prepared.

(Solution A-3) Ocein gelatin 34.0 g Distilled water 7779 ml Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% aqueous ethanol solution 20 ml 4-hydroxy-6-methyl-1,3,3a, 7-tetraaza Indene 405 mg 28% ammonia water 117.3 ml 56% acetic acid aqueous solution 72 ml Seed emulsion (EM-2) 0.303 mol equivalent (solution B-3) ossein gelatin 18.74 g KBr 760.2 g KI 28.4 g 4-hydroxy-6-methyl- 1,3,3a, 7- tetraaza indene 1.35g distilled water 1574 ml (solution E-3) to 1930ml with AgNO ₃ 1148 g 28% aqueous ammonia 937 ml distilled water.

(Solution F-3) 50% KBr aqueous solution, pAg adjustment required amount (Solution G-3) 56% acetic acid aqueous solution, pH adjustment required amount At 40 ° C, the mixing stirrer disclosed in JP-A-57-92523 and 57-92524 is used. Solution E-3 and solution B-3 were added to solution A-3 by the simultaneous mixing method, requiring a minimum time of 56.5 minutes without the generation of small particles on the way. PA during simultaneous mixing
The g, pH and addition rates of solutions E-3 and B-3 were controlled as shown in Table-3. The pAg and pH are controlled by solution F-3 and solution G- by a roller tube pump with variable flow rate.
3 and the solution B-3 were changed in flow rate.

Two minutes after the addition of the solution E-3 was completed, the solution G-3 was used to give pA.
g to 10.4 and after a further 2 minutes the pH is adjusted to 6 with solution F-3.
Adjusted to 0.

Next, deionized water is washed by a conventional method, and ossein gelatin is used.
After being dispersed in an aqueous solution containing 128.1 g, the total amount was adjusted to 3000 ml with distilled water.

By observation with an electron microscope, this emulsion has an average grain size of 0.80μ.
It was found that this was a highly monodisperse emulsion with a coefficient of variation of m and a grain size distribution of 10%.

(1-4) Addition of high-iodity shell, intermediate shell, and outermost shell of the present invention: The above-mentioned EM-3 was used as a seed emulsion by using the following seven kinds of solutions, and the high-iodity shell of the present invention, An emulsion EM-4 having an intermediate shell and an outermost shell was prepared.

(Solution A-4) Ocein gelatin 22.5 g Distilled water 6884 ml Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% aqueous ethanol solution 20 ml 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene Amount shown in Table-4 28% ammonia water 469 ml 56% acetic acid aqueous solution 258 ml Equivalent amount of seed emulsion 0.8828 mol (solution B-4) Ocein gelatin 24 g KBr Amount shown in Table-5 KI Amount shown in Table-5 4-hydroxy- 6-Methyl-1,3,3a, 7-tetraazaindene Amount described in Table-5 Distilled water 1978 ml (Solution C-4) Ocein gelatin 24 g KBr Amount described in Table-6 Amount described in KI Table-6 4-hydroxy -6-Methyl-1,3,3a, 7-tetraazaindene Amount shown in Table-6 Distilled water 1978 ml (Solution D-4) Ocein gelatin 4 The amount of 4-hydroxy-6-methyl amounts KI Table -7 description 0 g KBr table -7 described - 1,3,3a, 7- tetraaza indene Table -7 amount of distilled water 3296Ml (solution E-4) according AgNO ₃ 1109 g 28% ammonia water 904 ml Distilled water to 1866 ml.

(Solution F-4) 50% KBr aqueous solution, pAg adjustment required amount (Solution G-4) 56% acetic acid aqueous solution, pH adjustment required amount At 50 ° C., the mixing stirrer disclosed in JP-A-57-92523 and 57-92524 is disclosed. To solution A-4 using solutions E-4 and B-
4 and 4 were added by the simultaneous mixing method for 46.6 minutes, C-4 was added at the same time as the addition of B-4 was completed, D-4 was added at the same time as the addition of C-4 was completed after 35.9 minutes, and the addition was completed after 25.5 minutes. did. PAg, pH and solutions E-4, B during co-mixing
The addition rates of C-4, C-4 and D-4 were controlled as shown in Table-8. The pAg and pH were controlled by changing the flow rates of the solution F-4 and the solution G-4 using a roller tube pump having a variable flow rate.

2 minutes after the addition of the solution E-4 was completed, the solution F-4 gave a pA.
g to 10.4 and after a further 2 minutes the pH was adjusted to 6 with solution G-4.
Adjusted to 0.

Next, deionized water is washed by a conventional method, and ossein gelatin is used.
Dispersed in an aqueous solution containing 127g, then distilled water for a total volume of 3000m
Adjusted to 1.

By observation with an electron microscope, this emulsion has an average grain size of 1.60 μm.
It was found to be a highly monodisperse emulsion with a coefficient of variation of m and a grain size distribution of 11%.

EM-4 is 15 mol%, 5 mol% and
Core / shell type silver iodobromide emulsion having a silver iodide content of 0.3 mol% (that is, I _l = 0.3, I _h = 15, I _m = 5).
Is).

Production Example 2 Using 7 kinds of solutions shown in (1-4) of Production Example 1, K
Br, KI and 4-hydroxy-6-methyl-1,3,
3a, 7-tetraazaindene addition amount is shown in Tables 4,5 and
EM-5, EM-6, and EM-7 were produced in the same manner as in (1-4) of Production Example 1 except that the amounts described in 6 and 7 were used.

These were monodisperse emulsions having an average grain size of 1.60 μm, and the variation coefficients of grain size distribution were 17%, 15%, and 12%, respectively.

E. EXAMPLES Next, the present invention will be described in more detail with reference to examples.

<Example 1> The following layers are coated in order on a transparent support comprising a cellulose triacetate film subjected to an undercoating process and having an antihalation layer (containing 0.40 g of black colloidal silver and 3.0 g of gelatin). Sample 1 was thus prepared. In all of the following examples, the amount added to the light-sensitive material is shown per 1 m ² , and the silver halide emulsion and colloidal silver are shown in terms of silver.

Layer 1 ... 1.4 g of low-sensitivity red-sensitive silver iodobromide (containing 7 mol% of silver iodide) emulsion sensitized red-sensitive, 1.2 g of gelatin and 0.8 g of 1-hydroxy-4- (β -Methoxyethylaminocarbonylmethoxy-N- [δ- (2,4-di-
t-amylphenoxy) butyl] -2-naphthamide [hereinafter referred to as C-1. ], 0.075 g of 1-hydroxy-
4- [4- (1-hydroxy-δ-acetamide-3,
6-disulfo-2-naphthylazo) phenoxy] -N-
[Δ- (2,4-di-t-amylphenoxy) butyl-
2-naphthoamide disodium [hereinafter referred to as a colored cyan coupler (CC-1). ] And 0.015 g of 1-
Hydroxy-2 [δ- (2,4-di-t-amylphenoxy) n-butyl] naphthamide, 0.07 g of 4-octadecylsuccinimide-2- (1-phenyl-5-tetrazolylthio) -1-indanone [hereinafter DIR It is called the compound (D-1). ] A low-sensitivity red-sensitive emulsion layer (hereinafter referred to as RL layer) containing 0.65 g of tricresyl phosphate (TCP) dissolved therein.

Layer 2 ... 1.3 g of high-sensitivity red-sensitive silver iodobromide emulsion (EM-5),
1.2g gelatin and 0.21g cyan coupler (C-1)
And a high-sensitivity red-sensitive emulsion layer (hereinafter referred to as RH layer) containing 0.23 g of TCP in which 0.02 g of a colored cyan coupler (CC-1) was dissolved.

Layer 3 ... 0.07 g of 2,5-di-t-octylhydroquinone [hereinafter referred to as antifouling agent (HQ-1). ] 4 g of n-dibutyl phthalate [hereinafter referred to as DBP]. ] And an intermediate layer containing 0.8 g of gelatin (hereinafter referred to as IL).

Layer 4 ... 0.80 g of low-sensitivity silver iodobromide (containing 6 mol% silver iodide) emulsion sensitized to green and 2.2 g of gelatin;
0.8 g of 1- (2,4,6-trichlorophenyl) -3-
[3- (2,4-di-t-amylphenoxyacetamido) benzamide] -5-pyrazolone (hereinafter referred to as magenta coupler (M-1)), 0.15 g of 1- (2,4,6)
-Trichlorophenyl) -4- (1-naphthylazo)-
3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone [hereinafter referred to as colored magenta coupler (CM-1). ], A low-sensitivity green-sensitive emulsion layer (hereinafter referred to as GL) containing 0.95 g of TCP in which 0.016 g of DIR compound (D-1) was dissolved.

Layer 5: 1.8 g of high-sensitivity green-sensitive silver iodobromide (EM-5) emulsion, green-sensitized, 1.9 g of gelatin and 0.20 g of magenta coupler (M-1), and 0.049 g of colored A high-sensitivity green-sensitive emulsion layer (hereinafter referred to as GH) containing 0.25 g of TCP in which a magenta coupler (CM-1) was dissolved.

Layer 6 ... 0.15 g of yellow colloidal silver, 0.2 g of antifouling agent (H
A yellow filter layer (hereinafter referred to as YC) containing 0.11 g of DBP in which Q-1) was dissolved and 1.5 g of gelatin.

Layer 7: 0.2 g of low-sensitivity silver iodobromide (containing 4 mol% silver iodide) emulsion sensitized to blue and 1.9 g of gelatin and 1.5 g
Α-pivaloyl-α- (1-benzyl-2-phenyl-3,5-dioxoimidazolidin-4-yl) -2 ′
-Chloro-5 '-[α-dodecyloxycarbonyl) ethoxycarbonyl] acetanilide [hereinafter referred to as Y-1. ] A low-sensitivity blue-sensitive emulsion layer (hereinafter referred to as BL) containing 0.6 g of TCP.

Layer 8: 1.0 g of high-sensitivity silver iodobromide (E
M-5) High-sensitivity blue-sensitive emulsion layer (hereinafter referred to as BH) containing emulsion, 1.5 g of gelatin, and 0.65 g of TCP in which 1.30 g of yellow coupler (Y-1) was dissolved.

Layer 9 ... A protective layer having 2.3 g of gelatin (hereinafter referred to as PR).

Samples 2 to 6 having the same layer constitution as the sample 1 (layer constitution A), except for the emulsions of the high-speed emulsion layers (layer 2, layer 5 and layer 8) were prepared as follows.

The sample 7 was prepared in the same manner as the sample 1 described above, but the positions of the layers were changed as described below to prepare sample 7 (referred to as a layer structure B).

Layer 1 Same as sample 1 RL 2 〃 IL 〃 layer 3 〃 GL 〃 layer 4 〃 IL 〃 layer 5 〃 RH 〃 layer 〃 IL 〃 layer 7 〃 layer 〃 layer 〃 layer 〃 layer 〃 BH 〃 Layer 11 〃 PR 〃 Similar to Sample 7 above, Sample 8 in which only the emulsions of the high-sensitivity emulsion layers (layer 5, layer 7 and layer 10) were changed as follows:
Created ~ 12.

In addition, a sample 13 was prepared in the same manner as the sample 1 but the positions of the layers were changed as follows (a layer structure C).

Layer 1 Same as sample 1 RL 2 〃 IL 〃 layer 3 〃 GL 〃 layer 4 〃 IL 〃 layer 5 〃 BL 〃 layer 〃 IL 〃 layer 7 〃 layer 〃 〃 layer 〃 IL 〃 Layer 11 〃 BH 〃 Layer 12 〃 PR 〃 High sensitivity emulsion layer (Layer 7, Layer 9,
Samples 14 to 14 differing only the emulsion of layer 11) as follows:
18 created.

Each sample was subjected to wedge exposure according to a conventional method for measuring sensitometric performance and graininess, and subjected to rectangular wave frequency wedge exposure for measuring sharpness, and processed in the next processing step to obtain a dye image. The obtained characteristic values are shown in Table-9.

A high speed green sensitive emulsion layer containing 0.06 g of DNP (ditertiary nonylphenol) dispersion.

Second layer: 0.15 g of yellow colloidal silver and 0.2 g of antifouling agent dissolved
0.11 g of DBP (dibutyl terephthalate dispersion) and
Yellow filter layer containing 1.5 g gelatin.

In addition to the above composition, a gelatin hardening agent and a surfactant were added to each of the above two layers.

Each sample was subjected to wedge exposure according to a conventional method for measuring sensitometric performance (sensitivity, width of exposure area, fog) and graininess, and subjected to rectangular wave frequency wedge exposure for measuring sharpness, followed by the next treatment. Processed in process.

Treatment process: Color development image 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Used in each processing step The composition of the treatment liquid is shown below.

[Color developer]

 4-Amine-3-methyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.57g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g sodium bromide 1.3g nitrilotriacetic acid ・ 3 Sodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1.

[Bleaching solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to adjust the pH to 1 and adjust to pH 6.0 with ammonia water.

[Fixer]

 Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.6 g Sodium metabisulfite 2.3 g Water is added to adjust the pH to 1 and the pH is adjusted to 6.0 with acetic acid.

[Stabilizing liquid]

 Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add water to make 1.

B, G and R are measured values for blue, green and red light, respectively.

* 1 ... Sensitivity is shown as a relative value with the sensitivity of Sample No. 1 being 100.

* 2 ... MTF (Modula) is used to detect the effect of improving image sharpness.
spatial frequency is 10 lines / mm
It was carried out by comparing the magnitude of MTF in

* 3 ... RMS: Shows 1000 times the standard deviation of the variation in the density value that occurs when a dye image having a dye image density of Dmin + 0.8 is scanned with a microdensitometer having a circular scanning aperture of 25 μ.

From the above results, between the outermost shell (low iodine shell) and high iodine shell,
Conventional core / without intermediate shell with intermediate iodine content /
Shell emulsions (EM-5, EM-9) or cores with intermediate shells but with a sufficient difference in iodine content between the high iodine shell and the intermediate shell /
Compared with the shell emulsion (EM-6) and the core / shell emulsion (EM-8) which does not have a sufficient difference in iodine content between the outermost shell and the middle shell, the high iodine shell and the middle shell according to the present invention are used. , The core / shell emulsions having the outermost shells (EM-4, EM-7) have very high sensitivity.

Further, this effect is more remarkable in the multi-layer sensitivity, and it is understood that the core / shell emulsion of the present invention is more effective in the color light-sensitive material having the reverse layer structure (layer structure B, C).

<Example 2> EM-4, EM-5, EM-9 to EM-18 of the above Production Example.
Table 10 shows the effect of the iodine content of the high iodine shell in the same manner as in Example 1 (but with a layer structure of C).

Note that each value is only the characteristic value of the green-sensitive layer.

EM-10 to EM-15 have the same middle shell and outermost shell,
This is an example in which the iodine content of the high iodine shell is changed, and it can be seen that the higher the iodine content of the high iodine shell, the higher the sensitivity.

Emulsions with a high iodine content of 40 mol% or 50 mol% (E
In M-15 and EM-17), the sensitizing effect tends to be small, but this is thought to be due to the broad grain size distribution, and emulsions having the same high iodine shell (EM-16 and EM). -18)
It is understood that the emulsion of the present invention has a sufficient sensitizing effect as compared with the above.

<Example 3> Similarly, the effect of iodine content in the low-iodity shell and the intermediate shell is shown in Table-11.
Shown in.

The lower the iodine content of the outermost shell, the greater the sensitizing effect of the present invention.

In particular, the lower the iodide content of the outermost shell, the greater the effect on the layer sensitivity.

High iodine content of low iodine shell (10 mol% or more ... EM-2
6) The emulsion is less sensitive than the comparative emulsion.

<Example 4> Similarly, the effect of the particle size distribution is shown in Table-12.

The sensitizing effect of the present invention is more effectively obtained in a monodisperse emulsion having a narrow grain size distribution. The emulsion having a wide distribution is inferior to the emulsion having a narrow distribution in terms of fog and sharpness.

The monodisperse emulsion of the present invention is more preferable as an emulsion excellent in sensitivity, fog and sharpness.

<Example 5> Similarly, Table 13 shows the effect of the volume of the high iodine shell.

The sensitizing effect of the present invention is that the volume of the high iodine shell is 5% (EM-3
With a small amount of 3), it is sensitized but its effect is small, 12%
A more preferable effect is obtained in an emulsion having a relatively large volume of (EM-32), 22% (EM-33) and 41% (EM-34) high iodine shell.

<Example 6> Similarly, the effect of the total iodine content of the entire silver iodobromide is shown in Table-14.

In the present invention, emulsions having a relatively high total iodine content have a small sensitizing effect (EM-35, EM-36), and emulsions having a low total iodine content (EM-38) have graininess, sharpness and exposure. It is understood that it is preferable to use the emulsion of the present invention having an iodine content in an appropriate range in order to obtain high sensitivity, excellent graininess, sharpness, and a wide exposed area. .

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenji Kumadai, 1 Sakura Sakura-cho, Hino-shi, Tokyo Photo by Konishi Roku Photo Industry Co., Ltd. (72) Takashi Kamio 1 Sakura-cho, Hino-shi, Tokyo Photograph by Konishi Roku Photo Co., Ltd. (72) Inventor Toshifumi Iijima 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Industrial Co., Ltd. (56) Reference JP 59-204038 (JP, A) JP 46-1924 (JP, B1)

Claims (1)

[Claims] 1. A blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer is provided, and at least one of these silver halide emulsion layers comprises a plurality of layers having different sensitivities. Is composed of a low-sensitivity layer and a high-sensitivity layer, which are sequentially arranged from the support side, and at least one silver halide emulsion layer having different color sensitivity is disposed between these layers. At least one high-sensitivity layer of at least one silver halide emulsion layer, an internal core consisting essentially of silver bromide and / or silver iodobromide, and provided outside the internal core, and A negative type silver halide grain having a plurality of outer shells consisting essentially of silver bromide and / or silver iodobromide is contained, and the iodine content of the outermost shell of the silver halide grain is 10 mol. % And less than the outermost iodine 6 than the content rate
A silver halide photographic light-sensitive material characterized in that a shell having a high iodine content of more than mol% is provided inside the outermost shell.